Electronic spectroanalyzer systems



March 8, 1960 H. G. BuslGNlEs Erm. 2,927,501

ELECTRONIC sPEcTRoANALYzER SYSTEMS Filed March 13, 1956 i E mwws llitcd States ELECTRONIC SPECTROANALYZER SYSTEMS Application March 13, 1956, Serial No. 571,270 s Claims. (Cl. sis-14) This invention relates to spectroanalyzer systems for analyzing chemical compounds and mixtures and, more particularly, to spectroanalyzing methods and apparatus which overcome inherent nonlinearities in spectroanalytical equipment and the nonlinearity that may be present in the behavior of the chemical constituents contained in the compound or mixture.

In recent years, the absorption by compounds of nfrared energy at various points in the spectrum has been used for analytical purposes. In spite of the valuable information which can be obtained by the measurement of the infrared absorption of a sample, the use of this analytical tool has been greatly restricted due to certain practical dimculties. The infrared-absorption characteristic is dctermined by a spectrogram which is a graph of the percent of infrared radiation transmitted by the sample compound plotted against the wavelength of the radiation and normally shows several bands of relatively high infrared absorption which are characteristic of the atomic masses, the atomic bonds andthe molecular configuration in space of the sample being analyzed. While no two compounds have identical spectrograms, it is probable that the spectrograms of many related compounds have similarities including one or more similar absorption bands which coincide or partially overlap. Furthermore, the mean breadth of each absorption band, or, in other words, the frequency width of the spectrogram peak, increases as the quantity of the sample in the path of the radiation is increased thus increasing the amount of overlap between absorption bands. i One of the greatest diiculties presenting itself to the analyst is that the spectrograms of the individual constituents of a sample compound do not always add up in a truly linear manner to produce the spectrogram of the compound. Thus, the analyst must generally utilize a technique in order to determine the contents of the sample when the nonlinear behavior becomes troublesome. One technique heretofore utilized by those skilled in the art of spectroanalysis has been to eliminate from consideration that portion of the unknown spectrogram which is known to contain severe nonlinear behavior. Obviously, this entails some loss of information, but this loss normally is not serious since the elimination of a fraction only of the spectrum usually leaves sufficient data for reasonably accurate analysis. One alternate method of analysis used in the prior art was to dilute the sample compound; but while this resulted in a reduction of the nonlinear effects, it limited the accuracy since the dilution reduced the magnitude of the absorption spectrogram to the point where instrumental noise and inherent inaccuracies of the spectrophotometer became appreciable.

A second class of nonlinear eifects not due to the chemical effects of the compound is brought about by the inherent noise of the instruments used in the analysis. Thus, there are many instances where the simple methods used to overcome or to compensate for the known nonlineareiects are not effective; and thus, a different analytical system and/or process is required which is capable of atent CIC . taking into account or removing from the analytical results these nonlinear eifects.

One of the properties of conventional spectroanalysis is the lack of discrimination against nonlinear behavior of the elements in a chemical mixture, since the spectrogram of a chemical mixture contains the obscuring effects of the nonlinear behavior of its own constituents. It cannot be otherwise for the spectrogram merely relates in its own terms the occurrences of combination elects when various constituents are mixed together. If such a spectrogram is used as the basis for analysis, then it is:

clear that no linear combination of reference absorbance spectra can successfully match the absorbance spectrogram of the mixture. Thus, if extremely accurate analyses are to be established, some steps must be taken to include the effects of the nonlinear behavior within the data used for the calculation.

One of the objects of this invention is to provide a method and means for determining substantially the true ratio of the constituents in a chemical compound or mixture even though the combined constituents thereof involve a nonlinear behavior.

Another object is to provide an electronic spectroanalyzer system capable of analyzing chemical compounds or mixtures with a high degree of accuracy regardless of nonlinearities in the equipment of the system and nonlinearity behavior between constituents of the chemical compound or mixture. Y

One of the features of the invention involves the provision of an electronic spectroanalyst computer which analyzes an unknown mixture in terms of the linear combination of its constituent reference absorbance spectra. The linear ratio of the constituents thus obtained does not account for nonlinearity of equipment or nonlinearity of behavior in the combination of the constituents. These nonlinearities, however, are overcome or greatly minimized by synthesizing a sample of the ingredients according to the linear data obtained and comparing such sample with the unknown. This comparison is performed in a dual-beam spectrometer which provides a signal whose waveform represents a difference spectrum correspond'- ing to the nonlinearities existing between the unknown and the linear ratios obtained by the computer. This difference spectrum signal is then applied to the computer for analysis. The computer operates with the difference spectrum signal to obtain correction values for the ratio of constituents obtainedzin the first analysis. When this operation is completed the correction values are applied to a concentration computer which computes and deter-y mines what quantities are to be added to the synthetic sample to correct its concentration. When this correction of concentration is obtained in the sample at the dualbeam spectrometer a new comparison with the unknown is obtained giving a new difference, if any, between the corrected synthetic sample and the unknown. This new correction if signicant is applied again to the computer for analysis and when this is completed the concent-ration `computer corrects the recorded ratios accordingly. This operation may be repeated should the rst correction be insutlicient to account for all nonlinearities present. By such corrective operation the nonlinearities which are not detected by the computer in its original linear analysis of the unknown are now determined, thus' providing a highly accurate ratio indication of the constituents in the unknown.

The above-mentioned and other features and objects of this invention will become more apparent by reference to the following description taken in conjunction with the accompanying drawing, in which the single figure is a schematic diagram in block form of a spectroanalyzer vsystem in accordance with the principles of this invention.,

Asi-llustrated, the electronic spectroanalyzing computer esami 1 is shown coupled to the output of a dual-beam spectrometer '2;"by" means of'a' switch "3." 'The output of Ythe computer l is applied to a concentration computer 4 which in turn records and controls the preparation of a synthetic sampleaccording"to'they computed concentration ualues of the eonstituents ofthe 'compound ormixture beirut;analyzed.- Referring specifically to the computerfliga plurality of signal sources such as'5, 6 and 7 are 1shown representing the waveforms of absorbance spectra 'of reference chemicals f1, f2 to fn. iIt will be understood that in 'such 'a computer system the library ofsignal' sources -rwould involve a verylarge number of elements or even certain compounds from which informamay be drawn to determine the ratio of constituents ir'ra lllaartieular 'unknown compound or mixture. `Any suitable `storage means maybe provided to'store the ref .renee spectra and Whena signal is required the waveformjof the `spectrum is reproduced for use in the computer operation. The' signal waveforms produced by such sources as 5; 6and 7 are applied to controls 8,'9 and 10 which may be in the form of attenuator devices or other form'of signalV amplitude lcontrolling vmeans to pass the signal Waveform in the desired amplitude to the adder In analyzing a particular composition it should bel understood that the identities of the constituents of the I position mustfirst be known so that the signal referend "fsources for vthose constituents may be selected for use inanalyzing the ratio of'its constituents;

absorbance spectrum of a signal. Whose waveform characterizes the unknown composition may be fed directly from the spectrometer 2 through switch 3 to the subtractor circuit t2 or it may be applied from a previously obtained spectrogram from source 13. The controls such as 8f9 and 10 are representative of the ones selected to determiney the ratio of the constituents believed tobe contailned` in the unknown. This selection may be manual closingswitches 8a,'9a and 10a. The sum of the by outputs of attenuatorsv 8 9 and lil' is applied to the subtractor circuit 12 in comparison with the absorbance spectrum signal of the unknown and a difference signal' is"v obtained. rIhis difference'signal may be'viewed on a` monitor cathode ray tube"114, the differencel signalbeing alsoapplied to correlators 15, 16 and 17. The spectrum' signals'from sourcesjS, 6 and 7 are also applied over circuits 18, 19 and 2.0 to the"corrrelator s"1r5,`16 and 17Y The function of the correlators is to'determine' theerror' coeicients'attributabletoeach of'the concentration controis 8, 9'and litandV then by` feedback through circuits 21, '22 and 23 modify the attenuatingcharacteristics of the controls.' These error coefficients are obtained byl correlatingthe difference spectrum jL-f, where f is 'the spectrogram signal of the unknown sample andf is the:

spectrogram signal of the synthesized sample, with theV individual constituent spectrum signal such as f1,`for example, whereby an instantaneous product (f--fl is obtained.` The correlators also function as an integrator over 'a` desiredv 'ntegration 'period and operate by means of the feedback( circuits 21, 22 vand 23 to change the controls 8, 9` and 10 by'means` of motors 24, 25 and 26 thus adjusting the constituent ratios for re-appraisal through the adder'and subtractor circuits 11 and 12. This `cor relatior1-integration continues until the motorsV 24,25 and 26 come to a standstill at which point the constituent values correspond 'on a linear basis close to the true ratios of the constituents in the unknown.

For further information on the details and theory of operation of they spectrogram analyzing computer'l reference may be had to the copending application'of H. G; Busignies, M. Rogoi and G. A. Deschamps'SerialNo. 552,518, tiled December 12, v1955, now-'Patent No` 2;86 6,899. l

`A cycle control 27 of knownform is coupledrto each of the motors 24, 25 and 26 andY responds tothe simultaneous quiescent conditions ofthe motors A'apply' tit) control signal to gates 28, 29 and 30 through which the output ofVV the concentration controls 8, 9 and 10 are applied to the concentration computer 4. The concentration computer records the data received and determines the quantity of each constituent required to make a synthetic sample in accordance with the received inf0rmation. This quantity control is applied over circuits 31, 3'2 and 33 to valves 34, 35 and 36 which control the feed of the'constituentinaterialsthrough 'ducts 37, 3S and 39 to a synthetic sample container or cell 40. T he container 4t) is suitably shaped andpr'oportioned to receive a given minimum quantity fora sample to fill/the cell portion 41 which is subjected to an infraredbeam tol obtain the absorbance spectrum of the sample. The container 40 is preferably provided with a vibrating device 42 which is operated as desired toy suitably" mix the ingredients required for the sample. The container 4i), however, is adapted to receive additional quantities for correction purpsefs. .Y From' the foregoing description it is readily apparent that the conceritration computer 4 performs a rather simple"com"puting "operation that can be performed by any Vo'iioof 'several known types of computers. The cornputer 4 first receives the ratio data ofthe unknown composition which was derivedion a simultaneous linear basis by'co'mputer l.v 'This data is'recorded and utilizedy to determine` the lcuiantity of each constituent required to synthesize a sample of 'a given volume.' VThis concentration ratio data' is converted Vby the computer to a time basis for controlling the length of time the valves 34,v 35 and 36 are to be opened. 'The dual-beam'spectvrometer 2 of known form is shown to havefa sourcev of infraredvk light 43' focused` by means of mirrors 44`a`nd. 45 'through 'the windows of the containers`4t) andA 46 containing the synthetic sample andA the' unknown,' respectively. The absorbance spectra of the'two' beams are'p'as'sed' through a transmission filter 474 to" detectors 4S and 49Y which detect the voltage or temperature rise resultingV frornthe portions of the beams passing through "tliet'wo cellsiwlhe output of the two detectors is applied to 'a subtractor circuit which produces a" signal corresponding to the waveform difference ofthe detector outputsfThis diferenceabsorbance spectrum signaly maybe `viewed on a' cathode ray tube S0, the. spectrum signal being also applied'over circuit 51 to the difference spectrum input 52 for Vthe purpose of being analyzed in Vthe computer 1`.

Y The' computer(A 1v nowy analyzes the difference spectrum ooeiiicien't's in accordance with the linformationcontained` in the 'diierence`s`pectrum. vWhen the motors 24, 25 and 26 arrive at`a quiescent state the cycle control 27 operates' the gates 28, 29 and 30 to feed the correction data to the" concentration computer 4. Thecomputer 4 corrects thep'reviou'sly recordeddata accordingly'.

"Where a synthetic sample is req'u'ird 'according to this corrected' data, a new sample maybe made in container 40fbylremo`ving the old'sample and delivering new quantities"of`ing'redients thereto or thecomputer 4 may be employed to utilize the previous sample and merely' add. ingredients thereto suiiicient to lforr'n a new sample of larger volume having concentrations yof ingredients according tothe corrected ratios., "The corrected amounts are' applied to'the containerV 40 which is vibrated to mix the ingredients Vand thereby present a corrected concentration of thesample inthe cell portion'41. This correted sample' is'com'pared-with'the unknown andthe its applica tionA'over circuit'SI cause'the computer 1` tov s., spectrum which it passes on to the concentration computer 4 for readjustment of the values contained therein. This cyclic operation is performed one or more times as may be required until the difference spectrum is so minute that the result contained in the recording at computer 4 is suiciently accurate for use as the true value of the ratios of the constituents contained in the unknown.

While we have described above the principle of our invention in connection with specific apparatus it is to be clearly understood that this description is made only by way of example and not as a limitation to the scope of our invention as set forth in the objects thereof and in the accompanying claims.

We claim:

l. An electronic spectroanalyzer system for determining the ratio of the quantities of the constituents in a given composition in which the identities of the constit-A uents are known, comprising a spectrogram analyzing computer having a plurality of constituent refernece spectrograms for comparing7 the spectrogram of said composion with refrence spectrograms of said constituents to determine the approximate ratio of the quantities of said constituents present in said composition in terms of a linear combination of the constituents thereof, means included in said computer to translate respectively each of said spectrograms into an electrical signal whose waveform is representative thereof to effect the operations of said computer, means for synthesizing a sample mixture of said constituents in accordance with said approximate ratio, means for comparing the spectra of saidgiven composition and said sample mixture to obtain an elec trical signal whose waveform characterizes a diiference spectrum, means to apply said diierence spectrum signal to said spectrogram analyzing computer for comparison with said spectrogram signals of said constituents to obtain a set of correction coefficients, and means to adjust said approximate ratio in accordance with said correction coeicients to obtain substantially the true ratio of said constituents in said composition.

2. An electronic spectroanalyzer system for deter-v mining the ratio of the quantities of the constituents in a given composition in which the identities of the constituents are known, comprising a spectrogram analyzing computer having a plurality of reference spectrograms of elements, means to select thte reference spectrograms of elements constituting constituents of said composition, means to translate respectively each of said spectrograms into an elcetrical signal whose waveform is representative thereof, means to combine the selected spectrogram signals to form a composite spectrogram signal for determining the approximate ratio of the quantities of said constituents present in said composition, means for synthesizing a sample mixture of said constituents in accordance with said approximate ratio, means for generating a spectogram signal of said mixture and for comparing it with the spectrogram of said composition to obtain a dierence spectrogram signal, means to apply said difference spectrogram signal to said spectrogram analyzing computer for comparison with the spectrogram signals of said constituents to obtain a set of correction coeicients, and means to adjust said approximate ratio in accordance with said correction coeicients.

3. An electronic spectroanalyzer system for determining the ratio of the quantities of the constituents in a given composition in which the identities of the constituents are known, comprising a spectrogram analyzing computer having a plurality of constituents reference spectrograms for comparing the spectrogram of said composition with refrence spectrograms of said constituents to determine the approximate ratio of the quantities of said constituents present in said composition in terms of a linear combination of the constituents thereof, means included in said computer to translate respectively each of said spectrograms into an electrical signal whose Waveform is representative thereof to effect the operations of said computer, a concentration computer, cycle control means to applythe approximate ratio data of said spectrogram analyzing computer to said concentration computer for synthesizing a sample mixture of said constituents in accordance with said approximate ratio, means for comparing the spectra of said composition and said sample mixture to obtain a diifernece spectrum signal, and means to apply said difference spectrum signal to said spectrogram analyz-l ing computer for comparison with the spectrogram signals' of said constituents to obtain a set of correction coecients, said cycle control means operating to apply said correction coeiicients to said concentration computer to adjust the approximate ratio data contained therein.

4. An electronic spectroanalyzer system for determining the ratio of the quantities of the constituents in a given composition in which the identities of the constituents in a given composition in which the identities of the constituents are known, comprising a spectrogram analyzing computer having a plurality of constituent reference spectrograms for comparing the spectrogram of said composition with reference spectrograms of said constituents to determine the approximate ratio of the quantities of said constituents present in said composition in terms of a linear combination of the constituents thereof, means included in said computer to translate respectively each of said spectorgrams into an electrical signal whose waveform is representative thereof to efrect the operations of said computer, means for synthesizing a sample mixture of said constituents in accordance with said approximate ratio, a dualbeam spectrometer fOr comparing the spectra of said composition and said sample mixture to obtain a difference spectrum signal, means to apply said difference spectrum signal to said spectrogram analyzing computer for comparison with said spectrogram signals of said constituents to obtain a set of correction coefficients, and means to adjust said approxmate ratio in accordance with said correction coeiiicients.

5. An electronic spectroanalyzer system for determining the ratio of the quantities of the constituents in a given composition in which the identities of the constitents are known, comprising a spectrogram analyzing computer having a library of reference spectrograms of a plurality of elements, means for selecting the reference spectrograms corresponding to said constituents, means included in said computer to translate respectively each of said spectrograms into an electrical signal whose waveform is representative thereof to eiect the operations of said spectrogram computer, means to combine said selected spectrogram signals and compare the sum thereof with the spectrogram signal of said composition and correlators responsive to any difference to correct the selected reference spectrogram signals to determine the ratio of the quantities of the constituents in said composition in terms of a linear combination thereof, a concentration computer to record the ratio obtained and to compute the amounts of the constituents required to synthesize a mixture according to said ratio, a dual-beam spectrometer having a cell containing a specimen of said composition and a second cell for a sample mixture, means under control of said concentration computer to synthesize a sample mixture in said second cell in accordance with said ratio, means associated with said spectrometer to obtain a difference spectrum signal of the difference between the absorbance spectra of said composition and of said synthesized mixture, means to apply said diierence spectrum signal to said spectrogram analyzing computer to determine the quantities of said constituents represented in said diierence spectrum signal in terms of a linearcombination of said constituents to obtain a set of correction coefiicients, and means to An electronic spectroanalyzer system for determining ratio of thequantities of the constituents` in a given composition in which the identities of the constituents are`known, comprising a spectrograrn analyzing computer having a library of reference spectrograins of a plurality of elements, means for selecting from said library the reference spectrograms corresponding to said constituents, means included in said computer to translate respectively'each of said spectrograrns into an electrical signal whose waveform is nepresentativ,eI thereof to eiect the operations of said spectrograrn computer,` means to combiner the selected spectrograrn signals andk compare the sum thereof with the spectrogram signal of saidl cornposition to determine. the ratio of the quantities of the cnnstitnents in said` composition in terms of a linear Cmbnetign thereof, a goncemration Computer to recordl the'ratio obtained and to compute the amounts of the constituents required to synthesize a mixture according t9@ Said` tatie, means under Control 0f Said. Concentration computer to synthesize. a sample. mixture in accordance with. said ratio, means to compare the spectrum` ofsaicll mixture withk the spectrumvof said composition to, obtainlr ardiierence spectrum signal, means to apply saidv differ-- ence spectrum signal to said spectrogram analyzingcomfputer, to determine the quantities of said constituents rep-V resentedvin said diierence spectrum signal in` termS 0f 21, linear combination.` of said constituents to, obtain aser, of correction coeicients, and means. tot apply the output;` of said spectrogram analyzing computer to said concen tration computertoadjust they previously recordedl ratioy inY accordance with said setof correction coeiiicientm 7,. An electronic spectroanalyzer systernrfor determinf. ing the. ratio of the quantitiesfof the constituents in av given compositionin which the identities` of the. constitf. uents, arer'known, comprising a. spectrogram analyzing, computerihaving a library of reference spectrograms of. aupljuralityof elements, rneans for selecting the reference spectrograms corresponding to said constituentsL means. to generate a iirst signalhaving a waveshape representing the spectrogram of said composition, meansto generate afipl'urality of second signals each having a waveshape, representing one ottheselected reference spectra, means vsaiclsecondY signals to obtain a, composite spectrogram signal and tocompare it with the spectro;y gram signal of said composition to determine the ratio of.

to 'combm computer to record the ratio ohtaineddand to compiute theainounts of the` elementsrrequire'd to synthcsizeva,

the quantities of the constituents in said composition in terms of alinear combination thereof, av concentration,

i analyzing-computer to determine the quantities of said constituents represented in said difference spectrum signal in terms of a linear combination of said constituents to obtain a set of correction coefficients, and means to apply the output of said spectrogram analyzing computer to said concentration computer to adjust the previously recorded ratios, in accordance with said set of correction coeicients. i e

8.- A method for determining the ratio of the quantities of the constituents in a given composition wherein the identities of the constituents are known, comprising the steps of obtaining the. absorbance spectrogram of said compositiom obtaining the absorbancespectrograms of each of said known constituents,l generatingl a first signal having a waveshape representative of the absorbance; spectrograrn of said compositiom generating a plurality of, second signals each having a waveshape representative of onev of; the absorbance.. spectrograms of said constituents, combining` said plurality ofY second signals. in varionsv ratios to generate a composite spectrogram, comparing said composite spectrogram with the spectrogram of said composition and adjusting the values of said secoud Signals to obtain the optimum ratio of the combination of said plurality of second signals which yields acomposite. spectrogram having a least-squared diierence relative tothe spectrogram of said composition, chemically synthesizing a mixture of said constituents in ac-A cordance with,v said optimum ratio, producing a difference absorbance spectrogram from the difference betweenthe spectrograms of saidY composition and said chemically synthesized, mixture, generating a third signal having a waveshape representative of said` difference spectrogram,`

Comb.,

2,063,140, Allison Dec. 8, 1936. 2,462,995. Ritzmann Mar. 1, 1949,v 2,559,688, Touvet July 10, 1951,. 2,602,368l Barnes., July 8, i952:

OTHER REFERENCES Daly: A1A spectrometer for the analysisk of mixtures, usipgcathode-ray tube presentation of absorption differ ence spectra, pages 308-315, Journalsof Scientic In,-A

struments, May Y25, 1951, of,i Patent-` Otiice.)

(Copy in Scientilc Library fing said plurality of second signals in a second` rati which has theleast-squared difference relative to4 

